Cosmetic compositions containing an expoxidized oil as plasticizer

ABSTRACT

The invention relates to a cosmetic composition, for example, a nail varnish, comprising a film-forming material, at least one plasticizer comprising an epoxidized oil such as Vernonia oil and at least one solvent.

The present invention relates to a film-forming cosmetic composition,for example, nail varnish, colourless or coloured, containing, besidethe usual constituents, an epoxidized oil as a plasticizer.

Main characteristics of film-forming cosmetic compositions such as nailvarnishes, include, for example, the absence of irritation of thesupport, i.e., skin, nails and/or hair; good application; the obtainingof a homogeneous film having excellent gloss; a rapid drying time of thefilm, but also good adhesion to the surface of the support; and somedegree of flexibility and good strength of the film, for example, so asto avoid cracks and chipping of the film. These characteristics aregenerally designated cosmetic characteristics.

Generally speaking, film-forming materials such as nitrocellulose,combined, if necessary, with another polymer such as atoluenesulphonamide-formaldehyde resin or an alkyd resin andplasticizers, are used at the present time, for example, in nailvarnishes, to confer good adhesion and good flexibility of the film(see, in this connection, in particular, the document FR-A-2,679,445,the disclosure of which is specifically incorporated by referenceherein). The plasticizers commonly used are plasticizers of thephthalate type such as dibutyl phthalate; of the citrate type such astributyl acetylcitrate; of the glycol ester type such as neopentylglycol ester or propylene glycol ester; of the glyceryl benzoate type;and lastly, camphor. These plasticizing agents enable the flexibility ofthe film to be adjusted without weakening its physical strength.

Nowadays, it is preferable to use plasticizers other than phthalates invarnishes for reasons of allergy, but also other than camphor which,owing to its volatility, makes it difficult to achieve constant varnishcharacteristics. Moreover, it is preferable, and also for reasons ofallergy, to avoid the use of a polymer which is a source offormaldehyde.

For the purpose of applying varnish to the nails, liquid compositionscontaining a large amount of organic solvent (in general approximately70% by weight of the total composition) are used at the present time.Now, for reasons of pollution of the environment, it is sought todecrease the solvent amount.

Moreover, the formulation of nail varnishes is exacting, since thecomposition involves judicious matching between the differentconstituents. Thus, the change in one of these constituents canconsiderably modify the cosmetic properties of the varnish, such asapplication, gloss, drying, hardness or hold of the film, making thisvarnish unsuitable for use. For these reasons, the nail varnishformulations currently available on the market are virtually identicalor even identical.

The invention provides a new cosmetic composition which makes itpossible, in particular, to remedy the above drawbacks but still provideexcellent cosmetic properties.

The invention can also reduce or even eliminate the common plasticizersused in the prior art, and also reduce the amount of solvent.

The invention can also provide new hypoallergenic compositions.

Surprisingly, it was found that an epoxidized oil could be used as aplasticizer in cosmetic compositions containing an organic medium,without modifying the cosmetic properties of the film formed. This oilmay be used alone or, where appropriate, combined with anotherplasticizer known to a person skilled in the art.

More specifically, the invention relates to a cosmetic compositioncomprising at least one solvent, at least one film-forming material, aneffective amount of at least one plasticizer, wherein the plasticizercomprises at least one epoxidized oil, and wherein at least one of thefilm forming materials and at least one of the plasticizers aredifferent. This oil can be synthetic or, advantageously, natural.

As natural oils, vegetable oils such as epoxidized soya-bean oil,epoxidized linseed oil and, preferably, epoxidized Vernonia oil, as wellas mixtures thereof, may be mentioned. A preferred viscosity for suchsuitable epoxidized oils, particularly when the cosmetic composition ofthe invention is intended for use as a nail varnish composition, is inthe range from 200 to 400 mPa.s.

Vernonia oil, and more exactly that of Vernonia galamensis, is of thetriglyceride type whose general fatty acid composition is as follows:

    ______________________________________                                        vernolic acid                                                                              C 18:1 (unsaturated)                                                                        72.0-80.0%                                         palmitic acid                                                                              C 16:0        2.0-3.0%                                           stearic acid C 18:0        2.0-4.0%                                           oleic acid   C 18:1        4.0-6.0%                                           linoleic acid                                                                              C 18:2        11.0-14.0%                                         ______________________________________                                    

The Vernonia oil used in the present invention is a refined vegetableoil obtained by cold pressing of deactivated crushed Vernonia seeds.This refined oil is a transparent yellow homogeneous liquid which iscompletely soluble in most organic solvents. The advantage of this oilis its low viscosity (of the order of 300 mPa.s), which enables it to beintroduced in greater or lesser amounts without significantly modifying,relative to the traditional compositions, the viscosity of the medium.This low viscosity makes it possible, in addition, to decrease, relativeto the known compositions, the amount of solvent. To date, the onlyknown use of Vernonia oil is as a diluent in paints (see, in thisconnection, the article by S. Dirlikov et al., "Increasing high-solidswith a weed", Agro-industrial Finishing, p. 17-19).

The composition of the invention preferably contains, by weight, from0.5% to 25% of plasticizer, from 5% to 35% of film-forming materialother than the plasticizer and 40% to 90% of solvent, or in other words,solvent medium. More preferably, the composition of the inventioncontains from 3 to 15% of plasticizer, from 15% to 35% of film-formingmaterial other than the plasticizer and from 50% to 82% of solvent. Withthese compositions, it is possible to obtain dry extracts, i.e., thepercentage of the weight of the solid matter, such as film-formingcomponent and plasticizer in the cosmetic composition relative to thetotal weight of the composition, ranging from 20% to 50% by weight.Preferably, dry extracts are obtained which range from 20 to 40% byweight, more preferably from 25% to 40%, and most preferably from 20 to35%.

In addition, the epoxidized oil can be present at percentages greaterthan 9% by weight of the total composition in varnishes having a highdry extract without significantly modifying the viscosity, thus givingvarnishes having a reduced content of volatile products and possessingexcellent cosmetic characteristics.

Adjunct plasticizers which are usable in combination with the epoxidizedoil are, for example, those mentioned in the document FR-A-2,679,445,such as dibutyl, dioctyl, diisobutyl and dimethoxyethyl phthalates;benzyl and glyceryl benzoates; triethyl and tributyl citrates, tributylacetylcitrate; tributyl and triphenyl phosphates; glycols; and camphor,as well as their derivatives and mixtures thereof. These adjunctplasticizers represent at most 50% by weight of the total amount ofplasticizer.

The film-forming materials of the invention comprise especiallynitrocellulose, optionally combined with an alkyd, polyurethane,acrylic, vinyl, arylsulphonamide-formaldehyde or arylsulphonamide-epoxyresin, and, generally speaking, any resin compatible with the medium.These resins enable the film-forming power of nitrocellulose to beincreased and improve the gloss as well as the adhesion of the films.

The resin preferably combined with nitrocellulose is thetoluenesulphonamide-urea-formaldehyde resin better known under the tradenames "Santolite MHP", "Santolite MS 80%" and "Ketjenflex MS80". Thisresin possesses excellent film-forming properties. More preferably, theresin used is an alkyd resin, for example, of the glycerophthalic alkydtype (BECKOSOL ODE). Alkyd resins have the advantages of not containingformaldehyde and of being hypoallergenic.

Thus, preferably, the composition of the invention contains mainlynitrocellulose, an alkyd resin, Vernonia oil and at least one solvent.This composition possesses excellent cosmetic characteristics. It is, inaddition, possible to replace nitrocellulose by a polyvinyl resin suchas polyvinyl butyrate.

According to the invention, the solvent is preferably a mixture ofsolvents, and particularly a mixture of various volatile organicsolvents, the purpose of using volatile solvents being to obtainrelatively short drying times. The solvents used must be compatible withthe resins used in order to effect their dissolution.

preferred solvents are those traditionally used in cosmeticcompositions. Among these solvents, there may be mentioned ketones suchas acetone, methyl ethyl ketone, methyl isobutyl ketone; glycol ethers;alcohols such as ethanol, n-butanol, n-propanol, isopropanol; acetatessuch as butyl, ethyl and isopropyl acetate, 2-methoxyethyl acetate;linear or branched hydrocarbons such as hexane or octane; oralternatively, aromatic hydrocarbons such as xylene and toluene.Preferably, butyl and ethyl acetates are used.

When the cosmetic composition takes the form of a coloured nail varnish,at least one pigment of an organic or inorganic nature is then used.Among organic pigments, there may be mentioned D & C Red nos. 10, 11, 12and 13, D & C Red no. 7, D & C Red nos. 5 and 6, D & C Red no. 34, andlakes such as D & C Yellow no. 5 lake and D & C Red no. 2 lake. Guaninemay also be mentioned as an organic pigment.

Among inorganic pigments, titanium dioxide, bismuth oxychloride, browniron oxide and red iron oxides may be mentioned.

According to this embodiment, the pigments are generally present in aproportion ranging from 0.01% to 2.5% by weight relative to the totalweight of the varnish.

Moreover, in order to avoid sedimentation of the pigments, somethixotropic rheological agents may be employed, such as clays of the"Bentone 27", "Bentone 38" or montmorillonite type. These agents serve,in addition, as thickeners. Preferably, these agents are acidified usingcitric acid.

The nail varnishes according to the invention can, moreover, containadjuvants commonly used in nail varnishes. Among these adjuvants, theremay be mentioned UV screening agents such as benzophenone derivativesand ethyl 2 cyano-3,3-diphenylacrylate, colorants and also silicones andfluorinated agents. Preferably, these adjuvants are used at aconcentration at most equal to 1% by weight relative to the total weightof the varnish.

The compositions according to the invention can be mainly used as nailvarnishes. It is also possible to envisage using them as a make-upproduct, for example, mascara, or a hair-care product. In this case, thecompositions can contain, in addition, the constituents commonly used inthese applications, which constituents are well known to a personskilled in the art.

Several examples of nail varnish compositions according to the inventionwill now be given by way of illustration and without any impliedlimitation, together with comparative examples.

All the compositions below were obtained at room temperature, bysolubilizing nitrocellulose in the solvent (acetate), adding theepoxidized oil and then the alkyd or formaldehyde resin, and thendispersing the solid additives such as the clay type rheological agentsas well as citric acid and the pigments.

The nitrocellulose is used dissolved in isopropanol at a concentrationof 70% by weight. The alkyd resin (BECKOSOL ODE) and the formaldehyderesin (Santolite Ketjenlex MS80) are dissolved, respectively, at aconcentration of 70% by weight in xylene and 80% by weight in butylacetate.

The compositions are presented in the form of Tables I and II and, foreach composition, the amount of corresponding dry extract, their dryingtime and their viscosity are shown, together with the hardness, glossand surface energy of the films obtained. Tables I and II relate,respectively, to colourless nail varnishes and nail varnishes colouredred with D & C Red no. 7 pigment. D & C Red no. 7 was used in adispersion in the control colourless base (sample A) at 4% by weight.

Hardness is determined at the surface by measuring the time of swing ofa pendulum in contact with the film; it should be between 20 s and 150s, and preferably between 30 s and 80 s, in order to be satisfactory. Itis measured in a chamber thermostated at 30° C. with a constant 70%degree of humidity (RH).

Gloss corresponds to the coefficient of luminous reflection of the film;it should be greater than 75%, and preferably in the region of 90%.

The surface energy characterizes the surface of the film, and inparticular its capacity for wetting of the support.

Drying time is measured in an atmosphere controlled with respect totemperature (30° C.) and to humidity (50% RH), using a circular-motionball apparatus (Braive Instruments Model No. 55-50), wherein a ball,travelling in a circular motion, passes over the film of varnish 300 μmthick spread on a glass plate. It should be noted that the time measuredaccording to this technique is reproducible but greater than the dryingtime on a nail.

In Table I, it is seen that the characteristics of the films obtainedfrom the compositions B, D and G of the invention are comparable tothose obtained from the control compositions A, which contain Citroflexas plasticizer. Compositions C, E, and H are comparative compositions.

The composition C results in an excessively hard dry extract, since theamount of Vernonia oil is insufficient.

The composition E shows a fall in gloss and an increase in hardnessrelative to the compositions B and D, showing that Vernonia oil isbetter than linseed oil. It should be noted, however, that the linseedoil used here was non-epoxidized.

The composition H, for a higher dry extract than that of thecompositions A to G, indicates an insufficiency of the Vernonia oil as aresult of the viscosity and the great hardness. By increasing the amountof oil to more than 9% by weight of the composition, there is obtained,with a comparable dry extract, a composition I of the invention forwhich the viscosity goes down and the hardness of the film decreases. Oncomparing the composition I with the control composition J, it is seenthat their viscosity and their surface energy are comparable. On theother hand, the composition I of the invention is glossier than that ofcomposition J.

Thus, Vernonia oil is a good plasticizer of varnishes having a high dryextract.

In Table II, the samples Ac, Bc, Cc and Dc correspond to the samples A,B, C and D to which the pigment D & C Red no. 7 has been added. Fromthis Table II, it is seen that the addition of a pigment to thecompositions B, C and D causes little or no modification of theproperties of the nail varnish. The gloss, though slightly lower thanthat of the colourless compositions on account of the pigment, isentirely acceptable. In addition, these coloured compositions do notdisplay, 6 months after manufacture, any sedimentation of the pigment,and display good stability.

                                      TABLE I                                     __________________________________________________________________________    COLOURLESS                                                                             A          C        E    F           H         J                     SAMPLES  (CONTROL)                                                                            B   (COMP.)                                                                            D   (COMP.)                                                                            (CONTROL)                                                                            G    (COMP.)                                                                            I    (CONTROL)             __________________________________________________________________________    Nitrocellulose                                                                         14     14  16.66                                                                              14  14   14     14   18.83                                                                              17.5 17.5                  (70%)                                                                         ODE (70%)                                                                              15     15  17.84                                                                              15  15   --     --   20.17                                                                              18.75                                                                              18.75                 Santolite (80%)                                                                        --     --  --   --  --   13.125 13.125                                                                             --   --   --                    Citroflex                                                                              7.7    3.85                                                                              --   --  --   7.7    --   --   --   9.625                 Vernonia oil                                                                           --     3.85                                                                              3.85 7.7 --   --     7.7  7.7  9.625                                                                              --                    Linseed Oil                                                                            --     --  --   --  7.7  --     --   --   --   --                    Butyl acetate                                                                          36.78  36.78                                                                             35.79                                                                              36.78                                                                             36.78                                                                              37.905 37.905                                                                             30.78                                                                              31.275                                                                             31.275                Ethyl acetate                                                                          24.52  24.52                                                                             23.86                                                                              24.52                                                                             24.52                                                                              25.27  25.27                                                                              20.52                                                                              20.85                                                                              20.85                 Citric acid                                                                            0.5    0.5 0.5  0.5 0.5  0.5    0.5  0.5  0.5  0.5                   Bentone 27                                                                             1.5    1.5 1.5  1.5 1.5  1.5    1.5  1.5  1.5  1.5                   Dry Extract                                                                            28%    28% 28%  28% 28%  28%    28%  35%  35%  35%                   Nitro/resin ratio                                                                      0.93   0.93                                                                              0.93 0.93                                                                              0.93 0.93   0.93 0.93 0.93 0.93                  Viscosity mPa · s                                                             253    261 406  299 287  222    220  1038 693  675                   Hardness 30.4   48.0                                                                              163.3                                                                              50.4                                                                              137.9                                                                              21.9   49.6 78.1 50.9 31.0                  Gloss    88.00  87.6                                                                              87.7 86.2                                                                              81.9 91.3   95.7 87.8 90.4 85.2                  Surface energy                                                                         40.1   39.8                                                                              37.8 40.8                                                                              38.7 40.9   42.2 39.7 39.6 39.3                  Drying (min)                                                                           15     15  12.5                                                      __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________    COLOURED     Ac         Cc                                                    SAMPLES      (Control)                                                                          Bc    (COMPARATIVE)                                                                           Dc                                          __________________________________________________________________________    Nitrocellulose (70%)                                                                       12.6 12.6  14.994    12.6                                        ODE (70%)    13.5 13.5  16.056    13.5                                        Citroflex    6.93 3.465 --        --                                          Vernonia oil --   3.465 3.465     6.93                                        Butyl acetate                                                                              33.102                                                                             33.102                                                                              32.211    33.102                                      Ethyl acetate                                                                              22.068                                                                             22.068                                                                              21.474    22.068                                      Citric acid  0.45 0.45  0.45      0.45                                        Bentone 27   1.35 1.35  1.35      1.35                                        D & C Red no. 7 pigment                                                                    10   10    10        10                                          Dry Extract  28%  28%   28%       28%                                         Nitro/resin ratio                                                                          0.93 0.93  0.93      0.93                                        Hardness     32.8 45.7  156.6     62.0                                        Gloss        84.7 84.8  84.7      84.0                                        Surface energy                                                                             40.6 39.4  39.1      39.9                                        __________________________________________________________________________

We claim:
 1. A composition comprising from:(a) 0.5 to 25% of aplasticizer comprising an epoxidized oil, (b) 5 to 35% of a film-formingmaterial comprising nitrocellulose, and (c) 40-90% of a solvent ormixture of solvents.
 2. The composition according to claim 1, whereinthe epoxidized oil is Vernonia oil, soya-bean oil, or linseed oil. 3.The composition according to claim 2, wherein the epoxidized oil isVernonia oil.
 4. The composition according to claim 1, comprising, byweight, from 3% to 15% of a plasticizer, from 5% to 35% of film-formingmaterial comprising nitrocellulose, and from 50% to 82% of a solvent ormixture of solvents.
 5. The composition according to claim 1, whereinthe film-forming material comprises, in addition, at least onearylsulphonamide-formaldehyde resin, at least one alkyd resin, or amixture of at least one arylsulphonamide-formaldehyde resin and at leastone alkyd resin.
 6. The composition according to claim 1, comprisingnitrocellulose, an alkyd resin, Vernonia oil and a solvent medium. 7.The composition according to claim 1, wherein the composition furthercomprises at least one pigment.
 8. The composition according to claim 7,wherein said at least one pigment is present at a concentration of 0.01%to 2.5% by weight relative to the total weight of the composition. 9.The composition according to claim 1, wherein the composition is a nailvarnish composition.
 10. The composition according to claim 1, whereinthe solvent or solvents in the mixture comprise butyl acetate and ethylacetate.
 11. A method of coating a human nail comprising applying to thenail a film of an effective amount of a cosmetic composition comprisingan effective amount of at least one plasticizer, at least onefilm-forming material other than said plasticizer and a solvent, whereinthe plasticizer comprises at least one epoxidized oil.
 12. A method ofapplying mascara to a human eyelash comprising the step of applying tothe eyelash a mascara product containing an effective amount of acosmetic composition comprising an effective amount of at least oneplasticizer, at least one film-forming material other than saidplasticizer and a solvent, wherein the plasticizer comprises at leastone epoxidized oil.
 13. A method of treating human hair comprising thestep of applying to the hair a hair-care product containing an effectiveamount of a cosmetic composition comprising an effective amount of atleast one plasticizer, at least one film-forming material other thansaid plasticizer and a solvent, wherein the plasticizer comprises atleast one epoxidized oil.